JP2007332341A - Adhesive for pasting optically functional film, optically functional film and method for producing the same - Google Patents
Adhesive for pasting optically functional film, optically functional film and method for producing the same Download PDFInfo
- Publication number
- JP2007332341A JP2007332341A JP2006203589A JP2006203589A JP2007332341A JP 2007332341 A JP2007332341 A JP 2007332341A JP 2006203589 A JP2006203589 A JP 2006203589A JP 2006203589 A JP2006203589 A JP 2006203589A JP 2007332341 A JP2007332341 A JP 2007332341A
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- Prior art keywords
- adhesive
- functional film
- optical functional
- pressure
- sensitive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000853 adhesive Substances 0.000 title claims abstract description 123
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- 238000003860 storage Methods 0.000 claims abstract description 19
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- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133502—Antiglare, refractive index matching layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/38—Anti-reflection arrangements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本発明は、光学機能性フィルム貼合用粘着剤、光学機能性フィルム及びその製造方法に関する。 The present invention relates to an optical functional film laminating pressure-sensitive adhesive, an optical functional film, and a method for producing the same.
液晶表示パネルはＣＲＴに代わる表示装置として急速に普及し、その需要も拡大している。液晶表示パネルは、薄型で消費電力が小さいという利点を有する反面、ＣＲＴに比較して、輝度や視野角の点で不十分であるという欠点がある。そこで、バックライトを使用し、さらにパネル透過光を散乱させることでこれらを解決しようとする試みがなされてきた。
その一つとして、透明樹脂中に無機微粒子を分散させた光拡散粘着層を、液晶セルに設けることで視野角の拡大と表示品質を高める手法が提案されている（特許文献１、特許請求の範囲参照）。また、反射型液晶ディスプレイにおいても、透過した光を拡散させるために、光を拡散するためのフィラーを粘着剤に配合した拡散粘着層を液晶パネルに貼り合わせた液晶表示装置が提案されており、拡散粘着層の両面に離型シートを設けることが開示されている（特許文献２、特許請求の範囲参照）。
Liquid crystal display panels are rapidly spreading as a display device replacing CRT, and the demand for the liquid crystal display panel is expanding. The liquid crystal display panel has an advantage that it is thin and consumes less power, but has a drawback that it is insufficient in terms of luminance and viewing angle compared to a CRT. Therefore, attempts have been made to solve these problems by using a backlight and further scattering panel transmitted light.
As one of them, a method has been proposed in which a light diffusion adhesive layer in which inorganic fine particles are dispersed in a transparent resin is provided in a liquid crystal cell to increase the viewing angle and improve the display quality (
しかしながら、これらの液晶表示パネルは、光の拡散によって輝度むらが抑制され、均一な明るさが得られるものの、耐久性に劣るという問題があった。具体的には、液晶パネルの使用に際して、経時的に光拡散粘着層中に発泡が生じ、輝度むらが生じる。さらには、液晶セルに粘着剤を介して配置された偏光板や、視野角特性の改善を図るため、偏光板と液晶セルの間に粘着剤を介して配置された位相差板の経時による浮きや剥がれが発生する場合がある。また、拡散粘着層の両面に離型シートを設けた場合、拡散粘着層から一方の離型シートを剥離する際に拡散粘着層が他の粘着シートからも剥離してしまうこと（いわゆる泣き別れ）がある。 However, these liquid crystal display panels have a problem that the luminance unevenness is suppressed by light diffusion and uniform brightness is obtained, but the durability is inferior. Specifically, when the liquid crystal panel is used, foaming occurs in the light diffusion adhesive layer over time, resulting in uneven brightness. Furthermore, the polarizing plate placed in the liquid crystal cell via the adhesive and the retardation plate placed via the adhesive between the polarizing plate and the liquid crystal cell to improve the viewing angle characteristics float over time. Or peeling may occur. In addition, when release sheets are provided on both sides of the diffusion adhesive layer, the diffusion adhesive layer may also be released from the other adhesive sheet when peeling off one release sheet from the diffusion adhesive layer (so-called crying). is there.
本発明は、このような状況下で、光学機能性フィルムの接着、より具体的には偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板と液晶セルの接着、偏光板と位相差板の接着、位相差板相互の接着及び位相差板と液晶セルの接着に際して、耐久性よく接着し得ると共に、経時においても粘着層中の発泡や輝度むらが生じることがなく、液晶表示装置が均一な明るさとなる光学機能性フィルム貼合用粘着剤、光学機能性フィルム及びその製造方法、並びにいわゆる泣き別れが発生せず、光学機能性及びフィルムの貼合作業性に優れる粘着シートを提供することを目的とするものである。 Under such circumstances, the present invention provides adhesion of an optical functional film, more specifically, a polarizing plate integrated with a polarizing plate, particularly a viewing angle widening film, and a liquid crystal cell. When adhering the plates, adhering the phase difference plates, and adhering the phase difference plate and the liquid crystal cell, the liquid crystal display device can be bonded with good durability and does not cause foaming or uneven brightness in the adhesive layer over time. To provide a pressure-sensitive adhesive sheet excellent in optical functionality and film laminating workability without causing so-called crying separation, and a pressure-sensitive adhesive for optical functional film bonding with uniform brightness, an optical functional film and a method for producing the same. It is intended.
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、粘着性樹脂と微粒子を含有し、特定の貯蔵弾性率（Ｇ’）及びヘイズ値を有する粘着剤がその目的に適合し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
（１）粘着性樹脂と平均粒径０．１〜２０μｍの微粒子を含有する粘着剤であって、２３℃における貯蔵弾性率（Ｇ’）が、０．３〜１５ＭＰａであり、かつヘイズ値が５％以上である光学機能性フィルム貼合用粘着剤、
（２）８０℃における貯蔵弾性率（Ｇ’）が、０．３ＭＰａ以上である上記（１）に記載の光学機能性フィルム貼合用粘着剤、
（３）８０℃における貯蔵弾性率（Ｇ’）が、０．３〜１０ＭＰａである上記（２）に記載の光学機能性フィルム貼合用粘着剤、
（４）ゲル分率が６０％以上である上記（１）〜（３）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（５）前記光学機能性フィルムが偏光板及び／又は位相差板であり、偏光板と液晶ガラスセルの貼合、偏光板と位相差板の貼合、位相差板と位相差板の貼合又は位相差板と液晶ガラスセルの貼合に用いられる上記（１）〜（４）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（６）前記粘着性樹脂が（Ａ）アクリル系共重合体及び（Ｂ）活性エネルギー線硬化型化合物からなり、これに前記微粒子を分散させた粘着性材料に活性エネルギー線を照射してなる上記（１）〜（５）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（７）（Ｂ）成分の活性エネルギー線硬化型化合物が、分子量１０００未満の多官能（メタ）アクリレート系モノマーである上記（６）に記載の光学機能性フィルム貼合用粘着剤、
（８）多官能（メタ）アクリレート系モノマーが環状構造を有する上記（７）に記載の光学機能性フィルム貼合用粘着剤、
（９）多官能（メタ）アクリレート系モノマーがイソシアヌレート構造を有する上記（８）に記載の光学機能性フィルム貼合用粘着剤、
（１０）（Ａ）成分と（Ｂ）成分の含有割合が、質量比で１００：１〜１００：１００である上記（６）〜（９）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（１１）粘着性材料が、さらに（Ｃ）成分として架橋剤を含む上記（６）〜（１０）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（１２）粘着性材料が、さらに（Ｄ）成分としてシランカップリング剤を含む上記（６）〜（１１）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（１３）偏光板が偏光フィルムと視野角拡大フィルムとが一体化してなるものである上記（５）〜（１２）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（１４）無アルカリガラスに対する粘着力が０．２Ｎ／２５ｍｍ以上である上記（１）〜（１３）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（１５）８０℃における保持力が、７００００秒後のずれ量で２００μｍ以下である上記（１）〜（１４）のいずれかに記載の光学機能性フィルム貼合用粘着剤、
（１６）光学機能性フィルム上に上記（１）〜（１５）のいずれかに記載の粘着剤からなる層を有することを特徴とする粘着剤付き光学機能性フィルム、
（１７）剥離シートの剥離層上に設けられた粘着性材料層に光学機能性フィルムを貼合した後、剥離シート側から活性エネルギー線を照射することを特徴とする上記（１６）に記載の粘着剤付き光学機能性フィルムの製造方法、
（１８）２枚の剥離シートの剥離層側に接するように上記（１）〜（１５）のいずれかに記載の粘着剤を挟持してなる粘着シート、及び
（１９）上記（１８）に記載の粘着シートを用いて偏光板と位相差板を貼合する光学機能性フィルムの製造方法、
を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have found that a pressure-sensitive adhesive containing a pressure-sensitive adhesive resin and fine particles and having a specific storage elastic modulus (G ′) and haze value is suitable for the purpose. Found to get. The present invention has been completed based on such findings.
That is, the present invention
(1) An adhesive containing an adhesive resin and fine particles having an average particle size of 0.1 to 20 μm, having a storage elastic modulus (G ′) at 23 ° C. of 0.3 to 15 MPa, and a haze value 5% or more optical functional film bonding adhesive,
(2) The adhesive for optical functional film bonding according to the above (1), wherein the storage elastic modulus (G ′) at 80 ° C. is 0.3 MPa or more,
(3) The adhesive for optical functional film bonding according to the above (2), wherein the storage elastic modulus (G ′) at 80 ° C. is 0.3 to 10 MPa,
(4) The pressure-sensitive adhesive for optical functional film bonding according to any one of (1) to (3), wherein the gel fraction is 60% or more,
(5) The optical functional film is a polarizing plate and / or a retardation plate, bonding of a polarizing plate and a liquid crystal glass cell, bonding of a polarizing plate and a retardation plate, bonding of a retardation plate and a retardation plate. Or the adhesive for optical functional film bonding in any one of said (1)-(4) used for bonding of a phase difference plate and a liquid crystal glass cell,
(6) The above-mentioned pressure-sensitive adhesive resin is composed of (A) an acrylic copolymer and (B) an active energy ray-curable compound, and the pressure-sensitive adhesive material in which the fine particles are dispersed is irradiated with active energy rays. (1) -the adhesive for optical functional film bonding in any one of (5),
(7) The adhesive for optical functional film bonding according to the above (6), wherein the active energy ray-curable compound as the component (B) is a polyfunctional (meth) acrylate monomer having a molecular weight of less than 1000,
(8) The pressure-sensitive adhesive for optical functional film bonding according to (7), wherein the polyfunctional (meth) acrylate monomer has a cyclic structure,
(9) The pressure-sensitive adhesive for optical functional film bonding according to (8), wherein the polyfunctional (meth) acrylate monomer has an isocyanurate structure,
(10) Optical functional film bonding according to any one of the above (6) to (9), wherein the content ratio of the component (A) and the component (B) is 100: 1 to 100: 100 by mass ratio. Adhesive,
(11) The adhesive for optical functional film bonding according to any one of (6) to (10), wherein the adhesive material further contains a crosslinking agent as component (C),
(12) The adhesive for optical functional film bonding according to any one of (6) to (11), wherein the adhesive material further contains a silane coupling agent as the component (D),
(13) The pressure-sensitive adhesive for optical functional film bonding according to any one of (5) to (12), wherein the polarizing plate is formed by integrating a polarizing film and a viewing angle widening film,
(14) The pressure-sensitive adhesive for optical functional film bonding according to any one of the above (1) to (13), wherein the adhesive strength to an alkali-free glass is 0.2 N / 25 mm or more.
(15) The pressure-sensitive adhesive for optical functional film bonding according to any one of (1) to (14), wherein the holding power at 80 ° C. is 200 μm or less in terms of a deviation after 70000 seconds,
(16) An optical functional film with a pressure-sensitive adhesive comprising a layer made of the pressure-sensitive adhesive according to any one of (1) to (15) above on an optical functional film,
(17) The active energy ray is irradiated from the release sheet side after the optical functional film is bonded to the adhesive material layer provided on the release layer of the release sheet. Production method of optical functional film with adhesive,
(18) A pressure-sensitive adhesive sheet obtained by sandwiching the pressure-sensitive adhesive according to any one of (1) to (15) so as to be in contact with the release layer side of two release sheets, and (19) described in (18) above. The manufacturing method of the optical functional film which bonds a polarizing plate and a phase difference plate using the adhesive sheet of this,
Is to provide.
本発明の粘着剤によれば、光学機能性フィルムの接着、より具体的には偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板と液晶セルの接着、偏光板と位相差板の接着、位相差板と位相差板の接着及び位相差板と液晶セルの接着に際して、耐久性よく接着することができるとともに、液晶表示装置において、輝度むらがなく、均一な明るさを得ることができる。また、時間が経過しても粘着層中に発泡が生じることがなく、輝度むらが生じることもない。従って、本発明の粘着剤を用いることで、長期間にわたって、液晶表示装置が輝度むらのない、均一な明るさを保持することができる。 According to the pressure-sensitive adhesive of the present invention, adhesion of an optical functional film, more specifically, adhesion between a polarizing plate and a liquid crystal cell integrated with a polarizing plate, particularly a viewing angle widening film, Adhesion, adhesion between phase difference plate and phase difference plate, and adhesion between phase difference plate and liquid crystal cell can be bonded with good durability, and in a liquid crystal display device, uniform brightness can be obtained without uneven brightness. it can. Further, even if time elapses, foaming does not occur in the adhesive layer, and luminance unevenness does not occur. Therefore, by using the pressure-sensitive adhesive of the present invention, the liquid crystal display device can maintain uniform brightness without luminance unevenness over a long period of time.
本発明は光学機能性フィルム貼合用粘着剤に関するものであり、特には光学機能性フィルムの一種である偏光板と液晶セルの接着、偏光板と位相差板又は位相差板と位相差板などの光学機能性フィルム相互の接着、及び光学機能性フィルムの一種である位相差板と液晶セルの接着に用いる粘着剤に関する。
まず、液晶表示装置（ＬＣＤ）の液晶セルに偏光板を貼合して使用する場合について、図１を用いて説明する。
The present invention relates to a pressure-sensitive adhesive for bonding an optical functional film, in particular, adhesion between a polarizing plate and a liquid crystal cell, which are a kind of optical functional film, a polarizing plate and a retardation plate, or a retardation plate and a retardation plate. The present invention relates to a pressure-sensitive adhesive used for adhesion between optical functional films of each other, and a retardation plate which is a kind of optical functional film and a liquid crystal cell.
First, the case where a polarizing plate is bonded to a liquid crystal cell of a liquid crystal display device (LCD) will be described with reference to FIG.
液晶セル１３は、一般に配向層を形成した２枚の透明電極基板の配向層を内側にして、スペーサにより所定の間隔になるように配置し、その周辺をシールして、該間隔に液晶材料を挟持させると共に、上記２枚の透明電極基板に、それぞれ粘着剤１２を介して、偏光板１１が配置された講造を有している。前記偏光板は、一般的にポリビニルアルコール系偏光子の両面に、光学的等方性フィルム、例えばトリアセチルセルロース（ＴＡＣ）フィルムなどを貼り合わせた３層講造を有する偏光フィルムからなり、さらにその片面には、液晶セルなどの光学部品に貼着することを目的に粘着剤層が設けられている。本発明の粘着剤はこの粘着剤層の材料として好適に用いられるものである。
また、図２に示す模式図のように、視野角特性の改善を図るため、偏光板２１と液晶セル２３の間に粘着剤２２及び２５を介して位相差板２４が配置される場合がある。ここで使用される粘着剤２２及び２５として、本発明の粘着剤は好適に用いられるものである。
The
In addition, as shown in the schematic diagram of FIG. 2, a
本発明の光学機能性フィルム貼合用粘着剤は、粘着性樹脂と平均粒径０．１〜２０μｍの微粒子を主成分とする粘着剤により得られる。
粘着性樹脂としては、（Ａ）アクリル系共重合体と、（Ｂ）活性エネルギー線硬化型化合物からなるものが好ましく、これに前記微粒子を分散させた粘着性材料に活性エネルギー線を照射して得られた粘着剤が好ましい。
（Ａ）成分であるアクリル系共重合体としては、（メタ）アクリル酸エステル系共重合体を挙げることができる。なお、本発明において、（メタ）アクリル酸エステルとは、アクリル酸エステル及びメタクリル酸エステルの両方を意味する。他の類似用語も同様である。
The pressure-sensitive adhesive for bonding an optical functional film of the present invention is obtained from a pressure-sensitive adhesive mainly composed of a pressure-sensitive resin and fine particles having an average particle size of 0.1 to 20 μm.
The adhesive resin is preferably composed of (A) an acrylic copolymer and (B) an active energy ray-curable compound, and the adhesive material in which the fine particles are dispersed is irradiated with active energy rays. The obtained adhesive is preferred.
Examples of the acrylic copolymer as component (A) include (meth) acrylic acid ester copolymers. In the present invention, (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms.
前記（メタ）アクリル酸エステル系共重合体としては、各種架橋方法によって架橋が可能な架橋点を有するものが好ましく用いられる。このような架橋点を有する（メタ）アクリル酸エステル系共重合体としては特に制限はなく、従来粘着剤の樹脂成分として慣用されている（メタ）アクリル酸エステル系共重合体の中から、任意のものを適宣選択して用いることができる。 As the (meth) acrylic acid ester-based copolymer, those having a crosslinking point that can be crosslinked by various crosslinking methods are preferably used. There is no particular limitation on the (meth) acrylic acid ester-based copolymer having such a crosslinking point, and any (meth) acrylic acid ester-based copolymer conventionally used as a resin component of an adhesive can be arbitrarily selected. Can be selected and used.
このような架橋点を有する（メタ）アクリル酸エステル系共重合体としては、エステル部分のアルキル基の炭素数が１〜２０の（メタ）アクリル酸エステルと、分子内に架橋性官能基を有する単量体と、所望により用いられる他の単量体との共重合体を好ましく挙げることができる。ここで、エステル部分のアルキル基の炭素数が１〜２０の（メタ）アクリル酸エステルの例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチル、（メタ）アクリル酸ステアリルなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 As a (meth) acrylic acid ester-based copolymer having such a crosslinking point, a (meth) acrylic acid ester having an alkyl group of 1 to 20 carbon atoms and a crosslinkable functional group in the molecule. Preferable examples include copolymers of monomers and other monomers used as desired. Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, ( Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
一方、分子内に架橋性官能基を有する単量体は、官能基として水酸基、カルボキシル基、アミノ基、アミド基の少なくとも１種を含むことが好ましく、具体例としては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸３−ヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチルなどの（メタ）アクリル酸ヒドロキシアルキルエステル；（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミドなどのアクリルアミド類；（メタ）アクリル酸モノメチルアミノエチル、（メタ）アクリル酸モノエチルアミノエチル、（メタ）アクリル酸モノメチルアミノプロピル、（メタ）アクリル酸モノエチルアミノプロピルなどの(メタ)アクリル酸モノアルキルアミノエステル；アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸などのエチレン性不飽和カルボン酸などが挙げられる。これらの単量体は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 On the other hand, the monomer having a crosslinkable functional group in the molecule preferably contains at least one of a hydroxyl group, a carboxyl group, an amino group, and an amide group as a functional group. As a specific example, (meth) acrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic acid 4 -(Meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl; acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide; (meth) acrylic acid monomethylaminoethyl, (meta ) Monoethylaminoethyl acrylate, (meth) acrylic acid (Meth) acrylic acid monoalkylamino esters such as nomethylaminopropyl and (meth) acrylic acid monoethylaminopropyl; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid An acid etc. are mentioned. These monomers may be used independently and may be used in combination of 2 or more type.
当該粘着性材料において、（Ａ）成分として用いられる（メタ）アクリル酸エステル系共重合体は、その共重合形態については特に制限はなく、ランダム、ブロック、グラフト共重合体のいずれであってもよい。また、分子量としては、重量平均分子量で５０万以上であるものが通常用いられる。この重量平均分子量が５０万以上であると、被着体との密着性や接着耐久性が十分となり、浮きや剥がれなどが生じない。密着性及び接着耐久性などを考慮すると、この重量平均分子量は、６０万〜２２０万のものが好ましく、特に７０万〜２００万のものが好ましい。
なお、上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定したポリスチレン換算の値である。
In the adhesive material, the (meth) acrylic acid ester copolymer used as the component (A) is not particularly limited with respect to the copolymerization form, and may be any of random, block, and graft copolymers. Good. As the molecular weight, those having a weight average molecular weight of 500,000 or more are usually used. When the weight average molecular weight is 500,000 or more, adhesion to the adherend and adhesion durability are sufficient, and neither floating nor peeling occurs. In view of adhesion and adhesion durability, the weight average molecular weight is preferably 600,000 to 2,200,000, particularly preferably 700,000 to 2,000,000.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
さらに、この（メタ）アクリル酸エステル系共重合体においては、分子内に架橋性官能基を有する単量体単位の含有量は、０．０１〜１０質量％の範囲が好ましい。この含有量が０．０１質量％以上であると、後述する架橋剤との反応により、架橋が十分となり、耐久性が良好となる。一方、１０質量％以下であると、架橋度が高くなりすぎることによる、液晶ガラスセルや位相差板への貼合適性の低下がなく好ましい。耐久性と液晶ガラスセルや位相差板への貼合適性などを考慮すると、この架橋性官能基を有する単量体単位のより好ましい含有量は０．０５〜７．０質量％であり、特に０．２〜６．０質量％の範囲が好ましい。
本発明においては、この（Ａ）成分の（メタ）アクリル酸エステル系共重合体は１種用いてもよいし、２種以上を組み合わせて用いてもよい。
Furthermore, in this (meth) acrylic acid ester copolymer, the content of the monomer unit having a crosslinkable functional group in the molecule is preferably in the range of 0.01 to 10% by mass. When the content is 0.01% by mass or more, crosslinking is sufficient due to a reaction with a crosslinking agent described later, and durability is improved. On the other hand, when the content is 10% by mass or less, the degree of cross-linking becomes too high, and the suitability for bonding to a liquid crystal glass cell or a retardation plate is not deteriorated. Considering durability and suitability for bonding to a liquid crystal glass cell or a retardation plate, the more preferable content of the monomer unit having this crosslinkable functional group is 0.05 to 7.0% by mass, The range of 0.2-6.0 mass% is preferable.
In the present invention, the (meth) acrylic acid ester copolymer of the component (A) may be used alone or in combination of two or more.
当該粘着性材料において、（Ｂ）成分として用いられる活性エネルギー線硬化型化合物としては、分子量１０００未満の多官能（メタ）アクリレート系モノマーを好ましく挙げることができる。
この分子量１０００未満の多官能（メタ）アクリレート系モノマーとしては、例えば１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキサイド変性リン酸ジ（メタ）アクリレート、ジ（アクリロキシエチル）イソシアヌレート、アリル化シクロヘキシルジ（メタ）アクリレート、ジメチロールジシクロペンタンジ（メタ）アクリレート、エチレンオキサイド変性ヒドロフタル酸ジ（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、アダマンタンジ（メタ）アクリレート、９，９−ビス［４−（２−アクリロイルオキシエトキシ）フェニル］フルオレンなどの２官能型；トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレートなどの３官能型；ジグリセリンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレートなどの４官能型；プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレートなどの５官能型；ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレートなどの６官能型などが挙げられる。
In the adhesive material, as the active energy ray-curable compound used as the component (B), a polyfunctional (meth) acrylate monomer having a molecular weight of less than 1000 can be preferably exemplified.
Examples of the polyfunctional (meth) acrylate monomer having a molecular weight of less than 1000 include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate , Ethylene oxide modified di (meth) acrylate phosphate, di (acryloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate, dimethylol dicyclopentane di (meth) a Lilate, ethylene oxide modified hydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, adamantane di (meth) acrylate, 9,9-bis [4 Bifunctional type such as-(2-acryloyloxyethoxy) phenyl] fluorene; trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri Trifunctional type such as (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate; Tetrafunctional type such as tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; pentafunctional type such as propionic acid modified dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate and caprolactone modified dipentaerythritol Examples include hexafunctional types such as hexa (meth) acrylate.
本発明において、これらの多官能（メタ）アクリレート系モノマーは、１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよいが、これらの中で、骨格構造に環状構造を有するものを含有することが好ましい。環状構造は、炭素環式構造でも、複素環式構造でもよく、また、単環式構造でも多環式構造でもよい。このような多官能（メタ）アクリレート系モノマーとしては、例えばジ（アクリロキシエチル）イソシアヌレート，トリス（アクリロキシエチル）イソシアヌレートなどのイソシアヌレート構造を有するもの、ジメチロールジシクロペンタンジアクリレート、エチレンオキサイド変性ヘキサヒドロフタル酸ジアクリレート、トリシクロデカンジメタノールアクリレート、ネオペンチルグリコール変性トリメチロールプロパンジアクリレート、アダマンタンジアクリレートなどが好適である。 In the present invention, these polyfunctional (meth) acrylate monomers may be used alone or in combination of two or more. Among these, a cyclic structure is added to the skeleton structure. It is preferable to contain what it has. The cyclic structure may be a carbocyclic structure or a heterocyclic structure, and may be a monocyclic structure or a polycyclic structure. Examples of such polyfunctional (meth) acrylate monomers include those having an isocyanurate structure such as di (acryloxyethyl) isocyanurate, tris (acryloxyethyl) isocyanurate, dimethylol dicyclopentane diacrylate, ethylene Oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, adamantane diacrylate, and the like are suitable.
また、（Ｂ）成分として活性エネルギー線硬化型のアクリレート系オリゴマーを用いることができる。このようなアクリレート系オリゴマーの例としては、ポリエステルアクリレート系、エポキシアクリレート系、ウレタンアクリレート系、ポリエーテルアクリレート系、ポリブタジエンアクリレート系、シリコーンアクリレート系などが挙げられる。 Further, an active energy ray-curable acrylate oligomer can be used as the component (B). Examples of such acrylate oligomers include polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polybutadiene acrylates, and silicone acrylates.
ここで、ポリエステルアクリレート系オリゴマーとしては、例えば多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を（メタ）アクリル酸でエステル化することにより、あるいは、多価カルボン酸にアルキレンオキサイドを付加して得られるオリゴマーの末端の水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。エポキシアクリレート系オリゴマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂やノボラック型エポキシ樹脂のオキシラン環に、（メタ）アクリル酸を反応しエステル化することにより得ることができる。また、このエポキシアクリレート系オリゴマーを部分的に二塩基性カルボン酸無水物で変性したカルボキシル変性型のエポキシアクリレートオリゴマーも用いることができる。ウレタンアクリレート系オリゴマーは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアナートの反応によって得られるポリウレタンオリゴマーを、（メタ）アクリル酸でエステル化することにより得ることができ、ポリオールアクリレート系オリゴマーは、ポリエーテルポリオールの水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。
上記アクリレート系オリゴマーの重量平均分子量は、ＧＰＣ法で測定した標準ポリメチルメタクリレート換算の値で、５０，０００以下が好ましく、より好ましくは５００〜５０，０００、さらに好ましくは３，０００〜４０，０００の範囲で選定される。
これらのアクリレート系オリゴマーは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Here, examples of the polyester acrylate oligomer include esterification of hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to a monovalent carboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. It can be obtained by esterifying the hydroxyl group of ether polyol with (meth) acrylic acid.
The weight average molecular weight of the acrylate oligomer is a standard polymethyl methacrylate conversion value measured by GPC method, preferably 50,000 or less, more preferably 500 to 50,000, still more preferably 3,000 to 40,000. It is selected in the range.
These acrylate oligomers may be used alone or in combination of two or more.
本発明においては、（Ｂ）成分として（メタ）アクリロイル基を有する基が側鎖に導入されたアダクトアクリレート系ポリマーを用いることもできる。このようなアダクトアクリレート系ポリマーは、前述の（Ａ）成分の（メタ）アクリル酸エステル系共重合体において説明した（メタ）アクリル酸エステルと、分子内に架橋性官能基を有する単量体との共重合体を用い、該共重合体の架橋性官能基の一部に、（メタ）アクリロイル基及び架橋性官能基と反応する基を有する化合物を反応させることにより得ることができる。該アダクトアクリレート系ポリマーの重量平均分子量は、ポリスチレン換算で、通常５０万〜２００万である。
本発明においては、（Ｂ）成分として、前記の多官能アクリレート系モノマー、アクリレート系オリゴマー及びアダクトアクリレート系ポリマーの中から、適宜１種を選び用いてもよく、２種以上を選び併用してもよい。
In the present invention, an adduct acrylate polymer in which a group having a (meth) acryloyl group is introduced into the side chain can also be used as the component (B). Such an adduct acrylate-based polymer includes the (meth) acrylic acid ester described in the above-mentioned (meth) acrylic acid ester-based copolymer of the component (A), a monomer having a crosslinkable functional group in the molecule, And a compound having a (meth) acryloyl group and a group capable of reacting with a crosslinkable functional group is allowed to react with a part of the crosslinkable functional group of the copolymer. The weight average molecular weight of the adduct acrylate polymer is usually 500,000 to 2,000,000 in terms of polystyrene.
In the present invention, as the component (B), one type may be appropriately selected from the above polyfunctional acrylate monomers, acrylate oligomers and adduct acrylate polymers, or two or more types may be used in combination. Good.
本発明においては、前記（Ａ）成分のアクリル系共重合体と、（Ｂ）成分の活性エネルギー線硬化型化合物の含有割合は、得られる粘着剤の性能の面から、質量比で、１００：１〜１００：１００が好ましく、より好ましくは１００：５〜１００：５０、さらに好ましくは１００：１０〜１００：４０の範囲である。 In the present invention, the content ratio of the acrylic copolymer of the component (A) and the active energy ray-curable compound of the component (B) is 100% by mass from the aspect of the performance of the obtained adhesive. 1-100: 100 is preferable, More preferably, it is the range of 100: 5-100: 50, More preferably, it is the range of 100: 10-100: 40.
次に、本発明の粘着剤に用いられる微粒子は、光を拡散させるために用いられるもので、具体的には、シリカ、炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、クレー、タルク、二酸化チタン等の無機系白色顔料；アクリル樹脂、ポリスチレン樹脂、ポリエチレン樹脂、エポキシ樹脂、シリコーン樹脂等有機系の透明または白色顔料等をあげることができる。粘着性樹脂としてアクリル系共重合体を選択したときは、シリコーンビーズ、エポキシ樹脂ビーズ、ポリメチルメタクリレートビーズがアクリル系共重合体に対する分散性が優れ、均一で良好な光拡散性が得られることから好ましい。また、微粒子としては、光拡散が均一な球状の微粒子が好ましい。 Next, the fine particles used in the pressure-sensitive adhesive of the present invention are used for diffusing light. Specifically, silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, titanium dioxide, etc. Inorganic white pigments such as: organic transparent or white pigments such as acrylic resin, polystyrene resin, polyethylene resin, epoxy resin, and silicone resin. When an acrylic copolymer is selected as the adhesive resin, silicone beads, epoxy resin beads, and polymethylmethacrylate beads are excellent in dispersibility with respect to the acrylic copolymer, resulting in uniform and good light diffusibility. preferable. The fine particles are preferably spherical fine particles with uniform light diffusion.
該微粒子の平均粒径は０．１〜２０μｍの範囲である。平均粒径が０．１μｍ未満であると光拡散性が低下して、液晶表示装置において、輝度むらがなく、均一な明るさを得るという本発明の効果を達成することができない。一方、平均粒径が２０μｍを超えると、画像のコントラストに悪影響を与え、さらに、ディスプレイの画像ピッチより大きくなる場合にはギラツキが発生する。以上の点より、該微粒子の平均粒径は１〜１０μｍの範囲が好ましく、特に０．５〜１０μｍの範囲が好ましい。
なお、ここで微粒子の平均粒径は遠心沈降光透過法で測定した値である。測定には遠心式自動粒度分布測定装置（堀場製作所製「ＣＡＰＡ−７００」）を用い、微粒子１．２ｇとイソプロピルアルコール９８．８ｇからなる液を十分に撹拌したものを測定用試料とした。
The average particle diameter of the fine particles is in the range of 0.1 to 20 μm. When the average particle size is less than 0.1 μm, the light diffusibility is lowered, and in the liquid crystal display device, it is impossible to achieve the effect of the present invention in which there is no luminance unevenness and uniform brightness is obtained. On the other hand, if the average particle size exceeds 20 μm, the contrast of the image is adversely affected, and if it is larger than the image pitch of the display, glare occurs. From the above points, the average particle size of the fine particles is preferably in the range of 1 to 10 μm, and particularly preferably in the range of 0.5 to 10 μm.
Here, the average particle size of the fine particles is a value measured by a centrifugal sedimentation light transmission method. For the measurement, a centrifugal automatic particle size distribution measuring apparatus (“CAPA-700” manufactured by Horiba, Ltd.) was used, and a liquid consisting of 1.2 g of fine particles and 98.8 g of isopropyl alcohol was sufficiently stirred to be a measurement sample.
本発明の粘着剤における前記微粒子の含有量は１〜４０質量％の範囲が好ましい。この含有量が１質量％以上であると、輝度むらがなく、均一な明るさを得るという本発明の効果を達成することができ、一方、微粒子の含有量が４０質量％以下であると、粘着剤としての粘着力が確保される。 The content of the fine particles in the pressure-sensitive adhesive of the present invention is preferably in the range of 1 to 40% by mass. When the content is 1% by mass or more, the effect of the present invention can be achieved without uneven brightness and uniform brightness. On the other hand, when the content of fine particles is 40% by mass or less, Adhesive strength as an adhesive is ensured.
本発明の粘着性材料には、所望により光重合開始剤を含有させることができる。この光重合開始剤としては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−２−（ヒドロキシ−２−プロピル）ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４，４’−ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリ−ブチルアントラキノン、２−アミノアントラキノン、２−メチルチオキサントン、２−エチルチオキサントン、２−クロロチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、ｐ−ジメチルアミノ安息香酸エステル、オリゴ［２−ヒドロキシ−２−メチル−１［４−（１−メチルビニル）フェニル］プロパノン］、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイドなどが挙げられる。これらは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよく、また、その配合量は、前記（Ｂ）成分１００質量部に対して、通常０．２〜２０質量部の範囲で選ばれる。 The adhesive material of the present invention can contain a photopolymerization initiator as desired. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethyla Nobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl] propanone], 2, Examples include 4,6-trimethylbenzoyl-diphenyl-phosphine oxide. These may be used individually by 1 type, may be used in combination of 2 or more types, and the compounding quantity is 0.2-20 mass normally with respect to 100 mass parts of said (B) component. Selected in the range of parts.
また、本発明の粘着性材料には、所望により、（Ｃ）成分として架橋剤を含有させることができる。この架橋剤としては、特に制限はなく、従来アクリル系粘着剤において架橋剤として慣用されているものの中から、任意のものを適宜選択して用いることができる。このような架橋剤としては、例えばポリイソシアネート化合物、エポキシ樹脂、メラミン樹脂、尿素樹脂、ジアルデヒド類、メチロールポリマー、アジリジン系化合物、金属キレート化合物、金属アルコキシド、金属塩などが挙げられるが、ポリイソシアネート化合物が好ましく用いられる。 Moreover, the adhesive material of this invention can be made to contain a crosslinking agent as (C) component depending on necessity. There is no restriction | limiting in particular as this crosslinking agent, Arbitrary things can be suitably selected and used from what was conventionally used as a crosslinking agent in an acrylic adhesive. Examples of such crosslinking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, and metal salts. A compound is preferably used.
ここで、ポリイソシアネート化合物としては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族ポリイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂環式ポリイソシアネートなど、及びそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油などの低分子活性水素含有化合物との反応物であるアダクト体などを挙げることができる。 Here, as the polyisocyanate compound, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. And their biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Can do.
本発明においては、この架橋剤は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、その使用量は、架橋剤の種類にもよるが、前記（Ａ）成分のアクリル系共重合体１００質量部に対し、通常０．０１〜２０質量部、好ましくは、０．１〜１０質量部である。 In this invention, this crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, although the usage-amount is based also on the kind of crosslinking agent, it is 0.01-20 mass parts normally with respect to 100 mass parts of acrylic copolymers of the said (A) component, Preferably, it is 0.1-10. Part by mass.
さらに、本発明の粘着性材料には、所望により、（Ｄ）成分としてシランカップリング剤を含有させることができる。このシランカップリング剤を含有させることにより、偏光板等の光学機能性フィルムを、例えば液晶ガラスセルなどに貼合する場合に、粘着剤とガラスセルの間の密着性がより良好となる。このシランカップリング剤としては、分子内にアルコキシシリル基を少なくとも１個有する有機ケイ素化合物であって、粘着剤成分との相溶性がよく、かつ光透過性を有するもの、例えば実質上透明なものが好適である。このようなシランカップリング剤の添加量は、前記（Ａ）成分のアクリル系共重合体１００質量部に対し、０．００１〜１０質量部の範囲が好ましく、特に０．００５〜５質量部の範囲が好ましい。 Furthermore, the adhesive material of the present invention can contain a silane coupling agent as component (D) if desired. By including this silane coupling agent, when an optical functional film such as a polarizing plate is bonded to, for example, a liquid crystal glass cell, the adhesiveness between the pressure-sensitive adhesive and the glass cell becomes better. This silane coupling agent is an organosilicon compound having at least one alkoxysilyl group in the molecule, having good compatibility with the pressure-sensitive adhesive component, and having light transparency, for example, substantially transparent Is preferred. The addition amount of such a silane coupling agent is preferably in the range of 0.001 to 10 parts by mass, particularly 0.005 to 5 parts by mass with respect to 100 parts by mass of the acrylic copolymer of the component (A). A range is preferred.
前記シランカップリング剤の具体例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有ケイ素化合物、３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ構造を有するケイ素化合物、３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン等のアミノ基含有ケイ素化合物、３−クロロプロピルトリメトキシシラン等が挙げられる。これらは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the silane coupling agent include a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Silicon compounds having an epoxy structure such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- Examples include amino group-containing silicon compounds such as (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane. These may be used individually by 1 type and may be used in combination of 2 or more type.
本発明の粘着性材料には、本発明の目的が損なわれない範囲で、所望によりアクリル系粘着剤に通常使用されている各種添加剤、例えば粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、軟化剤などを添加することができる。 In the adhesive material of the present invention, various additives that are usually used in acrylic adhesives, for example, tackifiers, antioxidants, ultraviolet absorbers, light, as long as the purpose of the present invention is not impaired. Stabilizers, softeners and the like can be added.
本発明の光学機能性フィルム貼合用粘着剤は、このようにして得られた前記粘着性材料に、活性エネルギー線を照射してなるものである。
活性エネルギー線としては、例えば紫外線や電子線などが挙げられる。上記紫外線は、高圧水銀ランプ、無電極ランプ、キセノンランプなどで得られ、一方、電子線は電子線加速器などによって得られる。この活性エネルギー線の中では、特に紫外線が好適である。なお、電子線を使用する場合は、光重合開始剤を添加することなく、粘着剤を形成することができる。
当該粘着性材料に対する活性エネルギー線の照射量としては、後に詳述する貯蔵弾性率、無アルカリガラスに対する粘着力を有する粘着剤が得られるように、適宜選定されるが、紫外線の場合は照度５０〜１０００ｍＷ／ｃｍ2、光量５０〜１０００ｍＪ／ｃｍ2、電子線の場合は１０〜１０００ｋｒａｄの範囲が好ましい。
The pressure-sensitive adhesive for bonding an optical functional film of the present invention is obtained by irradiating the pressure-sensitive adhesive material thus obtained with active energy rays.
Examples of the active energy rays include ultraviolet rays and electron beams. The ultraviolet rays are obtained with a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp or the like, while the electron beam is obtained with an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. In addition, when using an electron beam, an adhesive can be formed, without adding a photoinitiator.
The irradiation amount of the active energy ray for the adhesive material is appropriately selected so as to obtain an adhesive having a storage elastic modulus, which will be described in detail later, and an adhesive force to an alkali-free glass. In the case of -1000 mW / cm < 2 >, the light quantity 50-1000 mJ / cm < 2 >, and an electron beam, the range of 10-1000 krad is preferable.
本発明の粘着剤は、２３℃における貯蔵弾性率（Ｇ’）が、０．３〜１５ＭＰａであることを要する。この貯蔵弾性率（Ｇ’）が０．３ＭＰａ未満であると粘着剤層中に発泡が生じ、輝度むらが生じたり、偏光板や位相差板等の光学機能性フィルムの経時による浮きや剥がれが発生する場合がある。一方、貯蔵弾性率（Ｇ’）が１５ＭＰａを超えると十分な接着耐久性が得られない。以上の観点から特に好ましい２３℃の貯蔵弾性率（Ｇ’）は０．３５〜１２ＭＰａであり、最も好ましくは０．５〜５ＭＰａである。
また、耐久性の点から８０℃の貯蔵弾性率（Ｇ’）も、通常０．３ＭＰａ以上が好ましく、さらには０．３〜１０ＭＰａ、特に０．４〜３ＭＰａであることが好ましい。
なお、前記貯蔵弾性率（Ｇ’）は、下記の方法で測定した値である。
The pressure-sensitive adhesive of the present invention requires a storage elastic modulus (G ′) at 23 ° C. of 0.3 to 15 MPa. When the storage elastic modulus (G ′) is less than 0.3 MPa, foaming occurs in the pressure-sensitive adhesive layer, resulting in uneven brightness, and floating or peeling of the optical functional film such as a polarizing plate or a retardation plate over time. May occur. On the other hand, when the storage elastic modulus (G ′) exceeds 15 MPa, sufficient adhesion durability cannot be obtained. From the above viewpoint, the storage elastic modulus (G ′) at 23 ° C. is particularly preferably 0.35 to 12 MPa, and most preferably 0.5 to 5 MPa.
Also, from the viewpoint of durability, the storage elastic modulus (G ′) at 80 ° C. is usually preferably 0.3 MPa or more, more preferably 0.3 to 10 MPa, and particularly preferably 0.4 to 3 MPa.
The storage elastic modulus (G ′) is a value measured by the following method.
＜貯蔵弾性率（Ｇ’）の測定方法＞
貯蔵弾性率（Ｇ’）は、厚さ３０μｍの粘着剤を積層し、８ｍｍφ×３ｍｍ厚の円柱状の試験片を作製し、ねじり剪断法により、下記の条件で測定する。
測定装置：レオメトリック社製動的粘弾性測定装置「ＤＹＮＡＭＩＣ ＡＮＡＬＹＺＥＲ ＲＤＡII」
周波数 ：１Ｈｚ
温度 ：２３℃、８０℃
<Method for measuring storage elastic modulus (G ′)>
The storage elastic modulus (G ′) is measured by the following conditions by laminating an adhesive having a thickness of 30 μm to produce a cylindrical test piece having a thickness of 8 mmφ × 3 mm and using a torsional shear method.
Measuring device: rheometric dynamic viscoelasticity measuring device "DYNAMIC ANALYZER RDAII"
Frequency: 1Hz
Temperature: 23 ° C, 80 ° C
次に、本発明の粘着剤はそのヘイズ値が５％以上である。ヘイズ値が５％以上であると画像コントラスト及び視認性が良好となる。ヘイズ値の上限については本発明の効果を奏する範囲であれば特に限定されないが、耐久性及び粘着物性の点から９０％以下が好ましい。以上の点から、ヘイズ値は２０〜９０％の範囲が好ましく、さらには３０〜７５％の範囲が好ましい。なお、ここでヘイズ値とは、ＪＩＳ Ｋ７１０５に準拠して測定される曇価であり、積分球式光線透過率測定装置を用いて、拡散透過率（Ｈｄ％）と全光線透過率（Ｈｔ％）を測定し、下記式にて算出する。
ヘイズ値＝Ｈｄ／Ｈｔ×１００
Next, the pressure-sensitive adhesive of the present invention has a haze value of 5% or more. When the haze value is 5% or more, the image contrast and the visibility are improved. The upper limit of the haze value is not particularly limited as long as the effect of the present invention is achieved, but 90% or less is preferable from the viewpoint of durability and adhesive properties. From the above points, the haze value is preferably in the range of 20 to 90%, more preferably in the range of 30 to 75%. Here, the haze value is a haze value measured in accordance with JIS K7105, and using an integrating sphere type light transmittance measuring device, diffuse transmittance (Hd%) and total light transmittance (Ht%). ) And measured by the following formula.
Haze value = Hd / Ht × 100
また、本発明の粘着剤はゲル分率が６０％以上であることが好ましい。すなわち、有機溶媒にて抽出される程度の低分子量成分が少ない場合は、加熱下や温熱下の環境で浮きや剥がれ、被着体への汚染が少なく、ゲル分率が６０％以上である粘着性材料は耐久性や安定性が高い。ゲル分率はさらに８５％以上であることが好ましく、特に９０〜９９．９％であることが好ましい。
本発明の光学機能性フィルム用粘着剤を用いて、例えば、液晶ガラスセル又は位相差板に偏光板を接着させることにより作製した液晶表示装置は、高温高湿環境下でも光漏れが生じにくい上、偏光板と液晶ガラスセルとの接着耐久性に優れている。
The pressure-sensitive adhesive of the present invention preferably has a gel fraction of 60% or more. That is, when there are few low molecular weight components that can be extracted with an organic solvent, the adhesive has a gel fraction of 60% or more because it floats and peels off in an environment of heating or heating, causes little contamination to the adherend. Material is highly durable and stable. The gel fraction is further preferably 85% or more, and particularly preferably 90 to 99.9%.
The liquid crystal display device produced by, for example, adhering a polarizing plate to a liquid crystal glass cell or a retardation plate using the optical functional film adhesive of the present invention is less likely to cause light leakage even in a high temperature and high humidity environment. Excellent adhesion durability between polarizing plate and liquid crystal glass cell.
また、本発明の光学機能性フィルム用粘着剤は、無アルカリガラスに対する粘着力が、０．２Ｎ／２５ｍｍ以上であることが好ましい。この粘着力が０．２Ｎ／２５ｍｍ以上であれば、偏光板等の光学機能性フィルムを十分な粘着力で、例えば液晶ガラスセルに貼合することができる。より好ましい粘着力は１．０〜５０Ｎ／２５ｍｍである。
また、ポリカーボネートに対する粘着力が、５Ｎ／２５ｍｍ以上であることが好ましい。この粘着力が５Ｎ／２５ｍｍ以上であれば、例えば偏光板を十分な粘着力で位相差板に貼合することができる。
なお、上記粘着力の測定方法については、後に詳述する。
本発明の光学機能性フィルム貼合用粘着剤は、８０℃における保持力が、７００００秒後のずれ量で２００μｍ以下であることが好ましい。このずれ量が２００μｍ以下であれば、偏光板等の光学機能性フィルムを、例えば液晶ガラスセルに貼合した場合に長期間にわたって良好な貼合状態を保持することができる。このずれ量は、より好ましくは１００μｍ以下である。
なお、上記ずれ量の測定（保持力の測定）方法については、後に詳述する。
Moreover, it is preferable that the adhesive force with respect to an alkali free glass of the adhesive for optical functional films of this invention is 0.2 N / 25mm or more. If this adhesive strength is 0.2 N / 25 mm or more, an optical functional film such as a polarizing plate can be bonded to, for example, a liquid crystal glass cell with sufficient adhesive strength. A more preferable adhesive force is 1.0 to 50 N / 25 mm.
Moreover, it is preferable that the adhesive force with respect to a polycarbonate is 5 N / 25mm or more. If this adhesive strength is 5 N / 25 mm or more, for example, the polarizing plate can be bonded to the retardation plate with sufficient adhesive strength.
The method for measuring the adhesive strength will be described in detail later.
The pressure-sensitive adhesive for bonding an optical functional film of the present invention preferably has a holding power at 80 ° C. of 200 μm or less in terms of a deviation after 70000 seconds. If this deviation | shift amount is 200 micrometers or less, when optical functional films, such as a polarizing plate, are bonded to a liquid crystal glass cell, a favorable bonding state can be hold | maintained over a long period of time. This deviation amount is more preferably 100 μm or less.
The method of measuring the amount of deviation (measuring holding force) will be described in detail later.
本発明の粘着剤は、光学機能性フィルムの貼合用に用いられ、特に、偏光板と液晶ガラスのセル、偏光板と位相差板、位相差板と位相差板又は位相差板と液晶ガラスのセルなどの貼合に好適に使用される。
より具体的には、偏光フィルム単独からなる偏光板に適用して、該偏光板を、例えば液晶ガラスセルに接着させるのに用いることができ、特に偏光フィルムと視野角拡大フィルムとが一体化してなる偏光板に適用し、この偏光板を、例えば液晶ガラスセルに接着させるのに、好ましく用いることができる。
The pressure-sensitive adhesive of the present invention is used for laminating optical functional films, and in particular, a polarizing plate and a liquid crystal glass cell, a polarizing plate and a retardation plate, a retardation plate and a retardation plate, or a retardation plate and a liquid crystal glass. It is suitably used for pasting of cells and the like.
More specifically, the present invention can be applied to a polarizing plate composed of a polarizing film alone and used to adhere the polarizing plate to, for example, a liquid crystal glass cell. In particular, the polarizing film and the viewing angle widening film are integrated. The polarizing plate can be preferably used for bonding to a liquid crystal glass cell, for example.
前記偏光フィルムと視野角拡大フィルムとが一体化してなる偏光板としては、例えばポリビニルアルコール系偏光子の両面に、それぞれトリアセチルセルロース（ＴＡＣ）フィルムを貼り合わせてなる偏光フィルムの片面に、例えばディスコティック液晶からなる視野角拡大機能層を塗布により設けたもの、あるいは視野角拡大フィルムを接着剤で貼り合わせたものなどを挙げることができる。この場合、粘着剤は、前記視野角拡大機能層又は視野角拡大フィルム側に設ける。 As the polarizing plate in which the polarizing film and the viewing angle widening film are integrated, for example, on one side of a polarizing film obtained by bonding a triacetyl cellulose (TAC) film to each side of a polyvinyl alcohol polarizer, for example, disco Examples thereof include those provided by applying a viewing angle widening functional layer made of a tick liquid crystal, and those obtained by bonding a viewing angle widening film with an adhesive. In this case, the adhesive is provided on the viewing angle widening functional layer or the viewing angle widening film side.
また、図２に示すように偏光板と液晶ガラスセルの間に位相差板がある場合にも、本発明の光学機能性フィルム用粘着剤は好適に使用し得る。すなわち、偏光フィルム単独からなる偏光板と位相差板を本発明の粘着剤で貼合して光学フィルムを製造し、該光学フィルムの位相差板と液晶ガラスセルを粘着剤で貼合するものである。
ここで、偏光板と位相差板を本発明の粘着剤で貼合している場合には、位相差板と液晶ガラスセルを貼合する粘着剤としては本発明の粘着剤以外のものを使用することもでき、特に限定されないが、本発明の粘着剤を用いることがより好ましい。なお、本発明の粘着剤以外の粘着剤としては、例えば、特開平１１−１３１０３３に開示されるアクリル系共重合体、架橋剤及びシラン化合物からなる粘着剤組成物などが挙げられる。
Moreover, also when there exists a phase difference plate between a polarizing plate and a liquid crystal glass cell as shown in FIG. 2, the adhesive for optical functional films of this invention can be used conveniently. That is, a polarizing plate and a retardation plate made of a polarizing film alone are bonded with the pressure-sensitive adhesive of the present invention to produce an optical film, and the phase difference plate of the optical film and a liquid crystal glass cell are bonded with a pressure-sensitive adhesive. is there.
Here, when the polarizing plate and the retardation plate are bonded with the pressure-sensitive adhesive of the present invention, as the pressure-sensitive adhesive for bonding the phase difference plate and the liquid crystal glass cell, those other than the pressure-sensitive adhesive of the present invention are used. Although not particularly limited, it is more preferable to use the pressure-sensitive adhesive of the present invention. Examples of the pressure-sensitive adhesive other than the pressure-sensitive adhesive of the present invention include a pressure-sensitive adhesive composition comprising an acrylic copolymer, a crosslinking agent and a silane compound disclosed in JP-A-11-133103.
本発明はまた、偏光板等の光学機能性フィルム上に、前述の本発明の粘着剤からなる層を有する粘着剤付き光学機能性フィルムをも提供する。より具体的には、粘着剤付き偏光板が挙げられ、この偏光板としては、前述したように、偏光フィルム単独からなるものであってもよいが、図１に示すような構成の場合には、偏光フィルムと視野角拡大フィルムとが一体化してなるものが好ましい。
なお、該粘着剤からなる層の厚さは、通常５〜１００μｍ程度、好ましくは１０〜５０μｍ、さらに好ましくは１０〜３０μｍである。
The present invention also provides an optical functional film with a pressure-sensitive adhesive having a layer made of the pressure-sensitive adhesive of the present invention on an optical functional film such as a polarizing plate. More specifically, a polarizing plate with an adhesive is mentioned, and this polarizing plate may be composed of a polarizing film alone as described above, but in the case of the configuration shown in FIG. A film formed by integrating a polarizing film and a viewing angle widening film is preferable.
In addition, the thickness of the layer which consists of this adhesive is about 5-100 micrometers normally, Preferably it is 10-50 micrometers, More preferably, it is 10-30 micrometers.
この粘着剤付き光学機能性フィルムの製造方法については、偏光板等の光学機能性フィルム上に本発明の粘着剤からなる層が設けられたものが得られる方法であればよく、特に制限はないが、以下に示す本発明の方法によれば、効率よく所望の粘着剤付き光学機能性フィルムを製造することができる。
本発明の方法においては、剥離シートの剥離層上に設けられた粘着性材料層に、偏光板等の光学機能性フィルムを貼合した後、該剥離シート側から活性エネルギー線を、前記粘着性材料層が、前述の所定の特性を有する本発明の粘着剤から構成される層になるように照射することによって、本発明の粘着剤付き光学機能性フィルムが得られる。
About the manufacturing method of this optical functional film with an adhesive, what is necessary is just a method by which what was provided with the layer which consists of an adhesive of this invention on optical functional films, such as a polarizing plate, There is no restriction | limiting in particular. However, according to the method of the present invention shown below, a desired optical functional film with a pressure-sensitive adhesive can be efficiently produced.
In the method of the present invention, an optical functional film such as a polarizing plate is bonded to the adhesive material layer provided on the release layer of the release sheet, and then the active energy ray is applied from the release sheet side to the adhesive. By irradiating the material layer so as to be a layer composed of the pressure-sensitive adhesive of the present invention having the above-mentioned predetermined characteristics, the optical functional film with the pressure-sensitive adhesive of the present invention is obtained.
前記剥離シートとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレンやポリエチレン等のポリオレフィンフィルムなどのプラスチックフィルムに、シリコーン樹脂などの剥離剤を塗布し剥離層を設けたものなどが挙げられる。この剥離シートの厚さについては特に制限はないが、通常２０〜１５０μｍ程度である。
また、粘着性材料及び活性エネルギー線の照射条件については、前述の本発明の光学機能性フィルム貼合用粘着剤において説明したとおりである。
剥離シート上に粘着性材料層を設ける方法としては、例えば、粘着性材料に溶剤を加えて、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などを用いて、粘着性材料をコーティングして塗膜を形成させ、乾燥させる方法を用いることができる。乾燥条件は特に制限されないが、通常５０〜１５０℃で１０秒〜１０分程度である。また、溶剤としては、例えば、トルエン、酢酸エチル、メチルエチルケトンなどが挙げられる。
Examples of the release sheet include a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., a plastic film such as a polyolefin film such as polypropylene or polyethylene, and a release layer such as a silicone resin applied to the release film. Is mentioned. Although there is no restriction | limiting in particular about the thickness of this peeling sheet, Usually, it is about 20-150 micrometers.
Moreover, about the irradiation conditions of an adhesive material and an active energy ray, it is as having demonstrated in the adhesive for optical functional film bonding of the above-mentioned this invention.
As a method of providing the adhesive material layer on the release sheet, for example, a solvent is added to the adhesive material, and a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like is used. Then, a method of coating an adhesive material to form a coating film and drying can be used. The drying conditions are not particularly limited, but are usually about 10 seconds to 10 minutes at 50 to 150 ° C. Examples of the solvent include toluene, ethyl acetate, methyl ethyl ketone, and the like.
また、図２に示すような構成の場合には、偏光板としては、偏光フィルム単独からなるものである場合が多く、偏光板用粘着剤からなる層の厚さは前記と同様である。図２に示すような構成における粘着剤付き偏光板の製造方法についても、上記と同様に偏光板上に本発明の粘着剤からなる層が設けられたものが得られる方法であればよく、特に制限はない。上記した本発明の製造方法によって効率的に製造することができる。
さらに、図２に示すような構成の場合には、２枚の剥離シートの剥離層側に接するように上述の偏光板用粘着剤（光学機能性フィルム貼合用粘着剤）を挟持してなる粘着シートを作製しておき、該粘着シートを用いて偏光板と位相差板を貼合することができる。ここで粘着剤として上記（Ｂ）成分を用いる場合には、活性エネルギー線は２枚の剥離シートに粘着性材料を挟持した後に照射してもよいし、一方の剥離シートに粘着性材料層を設け、活性エネルギー線を照射した後に他の剥離シートで挟持してもよい。なお、活性エネルギー線の照射条件は、前述の所定の特性を有する本発明の粘着剤から構成される層になるように選択される。
この２枚の剥離シートに挟持された粘着剤を用いて本発明の光学フィルムを製造する場合には、一方の剥離シートが剥がされ、通常の方法により偏光板あるいは位相差板と貼合される。
In the case of the configuration shown in FIG. 2, the polarizing plate is often made of a polarizing film alone, and the thickness of the layer made of the polarizing plate adhesive is the same as described above. As for the method for producing a polarizing plate with an adhesive in the configuration as shown in FIG. 2, any method can be used as long as it is a method in which a layer made of the adhesive of the present invention is provided on the polarizing plate as described above. There is no limit. It can manufacture efficiently by the manufacturing method of the above-mentioned this invention.
Furthermore, in the case of a structure as shown in FIG. 2, the above-mentioned pressure-sensitive adhesive for polarizing plate (pressure-sensitive adhesive for optical functional film bonding) is sandwiched so as to be in contact with the release layer side of the two release sheets. An adhesive sheet is prepared, and a polarizing plate and a retardation plate can be bonded using the adhesive sheet. Here, when the component (B) is used as an adhesive, the active energy ray may be irradiated after the adhesive material is sandwiched between two release sheets, or an adhesive material layer is applied to one release sheet. After providing and irradiating the active energy ray, it may be sandwiched between other release sheets. In addition, the irradiation conditions of an active energy ray are selected so that it may become a layer comprised from the adhesive of this invention which has the above-mentioned predetermined characteristic.
When the optical film of the present invention is produced using the adhesive sandwiched between the two release sheets, one release sheet is peeled off and bonded to a polarizing plate or a retardation plate by a normal method. .
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、実施例１〜８及び比較例１〜３で得られた粘着剤の性能、粘着剤付き偏光板の性能及び粘着シートの性能を、以下に示す要領で求めた。
（１）粘着剤の貯蔵弾性率
明細書本文に記載の方法に従って、２３℃及び８０℃における貯蔵弾性率を測定した。
（２）粘着力（無アルカリガラスに対する粘着力）
粘着剤付き偏光板から、２５ｍｍ幅、１００ｍｍ長のサンプルを２つ切り出し、剥離シートを剥がして（粘着剤層の厚さ２５μｍ）、無アルカリガラス［コーニング社製「１７３７」］に貼付したのち、栗原製作所製オートクレーブにて、０．５ＭＰａ、５０℃、２０分間の条件で加圧した。その後、２３℃、相対湿度５０％の環境下で２４時間放置したのち、同環境下で、引張試験機（オリエンテック社製テンシロン）を用いて、剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０°の条件で粘着力を測定した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the performance of the adhesive obtained in Examples 1-8 and Comparative Examples 1-3, the performance of the polarizing plate with an adhesive, and the performance of an adhesive sheet were calculated | required in the way shown below.
(1) Storage elastic modulus of adhesive The storage elastic modulus at 23 ° C. and 80 ° C. was measured according to the method described in the specification text.
(2) Adhesive strength (adhesive strength against non-alkali glass)
After cutting out two samples of 25 mm width and 100 mm length from the polarizing plate with an adhesive, peeling off the release sheet (
（３）ヘイズ値
粘着剤付きフィルムの剥離シートを剥離除去して、ＪＩＳ Ｋ７１０５に準拠し、積分球式光線透過率測定装置（日本電色工業製「ＮＤＨ−２０００」）を用いて、拡散透過率（Ｈｄ％）と全光線透過率（Ｈｔ％）を測定し、下記式にて算出した。
ヘイズ値＝Ｈｄ／Ｈｔ×１００
(3) Haze value The peeling sheet of the adhesive-attached film is peeled off and diffused and transmitted using an integrating sphere type light transmittance measuring device (“NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7105. The rate (Hd%) and the total light transmittance (Ht%) were measured and calculated by the following formula.
Haze value = Hd / Ht × 100
（４）ゲル分率
厚さ２５μｍの粘着剤を８０ｍｍ×８０ｍｍのサイズにサンプリングして、ポリエステル製メッシュ（メッシュサイズ２００）に包み粘着剤のみの重さを精密天秤にて秤量した。このときの重さをＭ１とする。ソックスレー（抽出器）を用いて酢酸エチル溶剤に粘着剤を浸漬させ、還流を行い１６時間処理した。その後粘着剤をとり出し、温度２３℃、相対湿度５０％の環境下、２４時間で風乾させ、さらに８０℃のオーブン中にて１２時間乾燥させた。乾燥後の粘着剤のみの重さを精密天秤にて秤量した。このときの重さをＭ２とする。（Ｍ２／Ｍ１）×１００（％)で表される値をゲル分率とする。
(4) Gel fraction A 25 μm thick adhesive was sampled to a size of 80 mm × 80 mm, wrapped in a polyester mesh (mesh size 200), and the weight of the adhesive alone was weighed with a precision balance. The weight at this time is M1. The pressure-sensitive adhesive was immersed in an ethyl acetate solvent using a Soxhlet (extractor), refluxed and treated for 16 hours. Thereafter, the pressure-sensitive adhesive was taken out, air-dried in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and further dried in an oven at 80 ° C. for 12 hours. The weight of only the pressure-sensitive adhesive after drying was weighed with a precision balance. The weight at this time is M2. The value represented by (M2 / M1) × 100 (%) is taken as the gel fraction.
（５）粘着剤付き偏光板の耐久性
粘着剤付き偏光板を、裁断装置（荻野精機製作所社製スーパーカッター「ＰＮ１−６００」）により、２３３ｍｍ×３０９ｍｍサイズに調整したのち、無アルカリガラス［コーニング社製「１７３７」］に貼合後、栗原製作所社製オートクレーブにて、０．５ＭＰａ、５０℃、２０分間の条件で加圧した。その後、下記の各耐久条件の環境下に投入し、２００時間後に、１０倍率ルーペを用いて観察を行い、以下の判定基準で耐久性を評価した。
○：４辺において、外周端部から０．６ｍｍ以上の領域に欠点がないもの。
×：４辺のいずれか１辺に、外周端部から０．６ｍｍ以上の領域に浮き、剥がれ、発泡、スジなどの０．１ｍｍ以上の粘着剤の外観異常欠点があるもの。
＜耐久条件＞
８０℃、９０℃、６０℃・相対湿度９０％環境、
−３０℃⇔７０℃の各３０分のヒートショック試験、２００サイクル
(5) Durability of polarizing plate with adhesive After adjusting the polarizing plate with adhesive to a size of 233 mm x 309 mm with a cutting device (Super cutter "PN1-600" manufactured by Sugano Seiki Seisakusho Co., Ltd.), alkali-free glass [Corning After being bonded to “1737” manufactured by Kogyo Co., Ltd., pressure was applied in an autoclave manufactured by Kurihara Seisakusho under the conditions of 0.5 MPa, 50 ° C. and 20 minutes. Then, it put into the environment of each following durability conditions, and after 200 hours observed using a 10 magnification loupe, and evaluated durability with the following criteria.
○: On the four sides, there is no defect in an area of 0.6 mm or more from the outer peripheral edge.
X: One of the four sides has an abnormal appearance defect of an adhesive of 0.1 mm or more such as floating, peeling, foaming, or streaking in an area of 0.6 mm or more from the outer peripheral edge.
<Durability conditions>
80 ℃, 90 ℃, 60 ℃, relative humidity 90% environment,
Heat shock test for 30 minutes each at -30 ° C to 70 ° C, 200 cycles
（６）保持力
粘着剤付きフィルムから、２５ｍｍ幅、１５０ｍｍ長のサンプルを切り出し、剥離シートを剥がして（粘着剤層の厚さ２５μｍ）、２５ｍｍ×２５ｍｍ（面積）が試験板に接するように貼付したのち、サンプルの上から２ｋｇのローラを速度３００ｍｍ／ｍｉｎで一往復させて、粘着剤層を試験板に圧着した。その後、２３℃、相対湿度５０％の環境下で２時間放置し、特開平１１−２３４４９号公報に記載の保持力測定装置を用い、荷重を１０００ｇとして、８０℃の環境下で、７００００秒後におけるずれ量を測定した。試験板としては、ＪＩＳ−Ｇ−４３０５に規定する厚さ１．５〜２．０ｍｍのＳＵＳ−３０４鋼板を、ＪＩＳ−Ｒ−６２５３に規定する３６０番の耐水性研磨紙で長さ方向に均一に研磨したものを使用した。また、保持力測定装置の測定センサーとしては、デジタルインジケーター（株式会社ミツトヨ製「DEGIMATIC INDICATOR」）を使用した。
（７）泣き別れの評価
長尺の粘着シートから、３００ｍｍ幅、２００ｍ長のロール状サンプルを２０本作製し、粘着剤層から第２の剥離シートを、剥離速度１０ｍ／ｍｉｎ又は３０ｍ／ｍｉｎで剥がしたときの第１の剥離シートと粘着剤層との間で部分的に剥離する現象（いわゆる泣き別れ）が発生したロール数（Ｘ）を求め、泣き別れ発生率（％）を、下記式にて算出した。
泣き別れ発生率＝Ｘ／２０×１００
(6)
(7) Evaluation of crying separation 20 roll-shaped samples having a width of 300 mm and a length of 200 m were prepared from a long pressure-sensitive adhesive sheet, and the second release sheet was peeled off from the pressure-sensitive adhesive layer at a peeling speed of 10 m / min or 30 m / min. The number of rolls (X) in which a phenomenon of partial peeling (so-called crying separation) occurred between the first release sheet and the pressure-sensitive adhesive layer was obtained, and the crying separation occurrence rate (%) was calculated by the following formula did.
Crying separation rate = X / 20 x 100
実施例１〜８及び比較例１〜３
第１表に示す組成（固形分）の粘着性材料（ａ）の酢酸エチル溶液（固形分１４質量％）を調製し、剥離シートとしての厚さ３８μｍのポリエチレンテレフタレート製剥離フィルム［リンテック社製「ＳＰ−ＰＥＴ３８１１」］の剥離層上に、乾燥後の厚さが２５μｍになるように、ナイフ式塗工機で塗布したのち、９０℃で１分間乾燥処理して粘着性材料層を形成した。
次いで、偏光フィルムと視野角拡大フィルムとが一体化した偏光板であるディスコティック液晶層付偏光フィルムのディスコティック液晶層と粘着性材料層とが接するように貼合した。貼合してから３０分後に剥離フィルム側から、紫外線（ＵＶ）を下記の条件で照射し、粘着剤付き偏光板を作製した。なお、第１表のシリコーンビーズの欄における（）内の数値は、粘着剤におけるシリコーンビーズの含有量（質量％）である。
＜ＵＶ照射条件＞
・フュージョン社製無電極ランプ Ｈバルブ使用
・照度６００ｍＷ／ｃｍ2、光量１５０ｍＪ／ｃｍ2
ＵＶ照度・光量計は、アイグラフィックス社製「ＵＶＰＦ−３６」を使用した。
Examples 1-8 and Comparative Examples 1-3
An ethyl acetate solution (solid content 14 mass%) of the adhesive material (a) having the composition (solid content) shown in Table 1 was prepared, and a release film made of polyethylene terephthalate having a thickness of 38 μm as a release sheet [manufactured by Lintec Corporation] On the release layer of SP-PET3811 "], after applying with a knife type coating machine so that the thickness after drying was 25 µm, it was dried at 90 ° C for 1 minute to form an adhesive material layer.
Subsequently, it bonded so that the discotic liquid crystal layer of the polarizing film with a discotic liquid crystal layer which is a polarizing plate which the polarizing film and the viewing angle expansion film were integrated, and the adhesive material layer may contact. 30 minutes after bonding, ultraviolet rays (UV) were irradiated from the side of the release film under the following conditions to prepare a polarizing plate with an adhesive. In addition, the numerical value in () in the column of silicone beads in Table 1 is the content (mass%) of the silicone beads in the adhesive.
<UV irradiation conditions>
Fusion Co. electrodeless lamp H bulb used, illuminance 600 mW / cm 2, light quantity 150 mJ / cm 2
“UVPF-36” manufactured by Eye Graphics Co., Ltd. was used as the UV illuminance / light meter.
また、ヘイズ値と保持力の測定に用いる粘着剤付きフィルムを以下のようにして作製した。上記の酢酸エチル溶液を、厚さ１００μｍのポリエチレンテレフタレートフィルム［東洋紡績社製「コスモシャインＡ４１００」］に、乾燥後の厚さが２５μｍになるように、ナイフ式塗工機で塗布したのち、９０℃で１分間乾燥処理して粘着性材料層を形成した。次いで、剥離シートとしての厚さ３８μｍのポリエチレンテレフタレート製剥離フィルム［リンテック社製「ＳＰ−ＰＥＴ３８１１」］の剥離層と上記粘着性材料層を貼合し、貼合してから３０分後に剥離フィルム側から、上記と同様の条件で紫外線を照射し、粘着剤付きフィルムを作製した。
さらに、粘着シートを以下のようにして作製した。上記の酢酸エチル溶液を、第１の剥離シートとしての厚さ３８μｍのポリエチレンテレフタレート製剥離フィルム［リンテック社製「ＳＰ−ＰＥＴ３８１１」］の剥離層上に、乾燥後の厚さが２５μｍになるように、ナイフ式塗工機で塗布したのち、９０℃で１分間乾燥処理して粘着性材料層を形成した。
次いで、第２の剥離シートとして厚さ３８μｍのポリエチレンテレフタレート製剥離フィルム［リンテック社製「ＳＰ−ＰＥＴ３８０１」］を用い、第２の剥離シートの剥離層と上記粘着材料層が接するように貼合した。貼合してから３０分後に第１の剥離シート側から、紫外線を上記と同様の条件で照射し、２枚の剥離シートの剥離層側に接するように粘着剤を挟持してなる長尺の粘着シートを作製した。
粘着剤の性能、粘着剤付き偏光板の性能及び粘着シートの性能の評価結果を第２表に示す。
Moreover, the film with an adhesive used for the measurement of a haze value and holding power was produced as follows. The above ethyl acetate solution was applied to a 100 μm thick polyethylene terephthalate film [“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.] with a knife coater so that the thickness after drying was 25 μm. A pressure-sensitive adhesive material layer was formed by drying at 1 ° C. for 1 minute. Next, a release layer of a polyethylene terephthalate release film [SP-PET3811 made by Lintec Co., Ltd.] having a thickness of 38 μm as a release sheet is bonded to the adhesive material layer, and the release film side is 30 minutes after bonding. Then, ultraviolet rays were irradiated under the same conditions as described above to produce a film with an adhesive.
Furthermore, an adhesive sheet was prepared as follows. On the release layer of the release film made of polyethylene terephthalate having a thickness of 38 μm as the first release sheet [“SP-PET3811” manufactured by LINTEC Co., Ltd.] as the first release sheet, the thickness after drying becomes 25 μm. After applying with a knife type coating machine, the adhesive material layer was formed by drying at 90 ° C. for 1 minute.
Next, a 38 μm thick polyethylene terephthalate release film [“SP-PET 3801” manufactured by Lintec Co., Ltd.] was used as the second release sheet, and bonded so that the release layer of the second release sheet was in contact with the adhesive material layer. . 30 minutes after bonding, from the first release sheet side, ultraviolet rays are irradiated under the same conditions as described above, and the adhesive is sandwiched so as to be in contact with the release layer side of the two release sheets. An adhesive sheet was prepared.
Table 2 shows the evaluation results of the performance of the pressure-sensitive adhesive, the performance of the polarizing plate with the pressure-sensitive adhesive, and the performance of the pressure-sensitive adhesive sheet.
（注）
１）アクリル系共重合体：アクリル酸ブチル及びアクリル酸を、質量比９５：５の割合で用い、常法に従って重合してなる、重量平均分子量１８０万の共重合体
２）多官能アクリレート系モノマー：トリス（アクリロキシエチル）イソシアヌレート、分子量＝４２３、３官能型（東亜合成社製、商品名「アロニックスＭ−３１５」）
３）光重合開始剤：ベンゾフェノンと１−ヒドロキシシクロヘキシルフェニルケトンとの質量比１：１の混合物、チバ・スペシャルティ・ケミカルズ社製「イルガキュア５００」
４）イソシアネート系架橋剤：トリメチロールプロパン変性トリレンジイソシアネート（日本ポリウレタン社製「コロネートＬ」）
５）シランカップリング剤：３−グリシドキシプロピルトリメトキシシラン（信越化学工業社製「ＫＢＭ−４０３」）
６）シリコーンビーズ：真球状シリコーン微粒子（ＧＥ東芝シリコーン社製「トスパール１４５」、平均粒径４．５μｍ）
(note)
1) Acrylic copolymer: butyl acrylate and acrylic acid in a mass ratio of 95: 5, polymerized according to a conventional method, and having a weight average molecular weight of 1.8 million 2) Multifunctional acrylate monomer : Tris (acryloxyethyl) isocyanurate, molecular weight = 423, trifunctional type (trade name “Aronix M-315” manufactured by Toa Gosei Co., Ltd.)
3) Photopolymerization initiator: mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1: 1, “Irgacure 500” manufactured by Ciba Specialty Chemicals
4) Isocyanate-based cross-linking agent: trimethylolpropane-modified tolylene diisocyanate (“Coronate L” manufactured by Nippon Polyurethane)
5) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)
6) Silicone beads: Spherical silicone fine particles (“Tospearl 145” manufactured by GE Toshiba Silicones, average particle size: 4.5 μm)
７）糊残りが認められる。 7) Adhesive residue is observed.
本発明の光学機能性フィルム貼合用粘着剤によれば、光学機能性フィルムの接着、より具体的には偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板と液晶セルの接着、偏光板と位相差板の接着、位相差板と位相差板の接着及び位相差板と液晶セルの接着に際して、耐久性よく接着することができるとともに、液晶表示装置において、輝度むらがなく、均一な明るさを得ることができる。また、時間が経過しても粘着層中に発泡が生じることがなく、輝度むらが生じることもない。従って、本発明の粘着剤を用いることで、長期間にわたって、液晶表示装置が輝度むらのない、均一な明るさを保持することができる。また、本発明の粘着剤を２枚の剥離シートで挟持した粘着シートは、いわゆる泣き別れが発生せず、光学機能性フィルムの貼合作業性に優れる。 According to the optical functional film laminating pressure-sensitive adhesive of the present invention, adhesion of an optical functional film, more specifically, a polarizing plate formed by integrating with a polarizing plate, particularly a viewing angle widening film, and a liquid crystal cell, It is possible to bond with good durability when bonding the polarizing plate and the retardation plate, between the retardation plate and the retardation plate, and between the retardation plate and the liquid crystal cell. Brightness can be obtained. Further, even if time elapses, foaming does not occur in the adhesive layer, and luminance unevenness does not occur. Therefore, by using the pressure-sensitive adhesive of the present invention, the liquid crystal display device can maintain uniform brightness without luminance unevenness over a long period of time. Moreover, the adhesive sheet which pinched | interposed the adhesive of this invention with two peeling sheets does not generate | occur | produce so-called tearing, and is excellent in the bonding workability | operativity of an optical functional film.
１，２；液晶表示装置
１１，２１；偏光板
１２，２２，２５；粘着剤
１３，２３；ガラス（液晶セル）
２４；位相差板
1, 2; Liquid
24; retardation plate
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| JP2006203589A JP4953717B2 (en) | 2006-05-19 | 2006-07-26 | Optical functional film bonding adhesive, optical functional film and method for producing the same |
| US11/746,830 US8388798B2 (en) | 2006-05-19 | 2007-05-10 | Pressure-sensitive adhesive for applying optically functional film, optically functional film and production process for the same |
| KR1020070045544A KR101234931B1 (en) | 2006-05-19 | 2007-05-10 | Pressure-sensitive adhesive for applying optically functional film, optically functional film and production process for the same |
| CN2007100973769A CN101074349B (en) | 2006-05-19 | 2007-05-11 | Pressure-sensitive adhesive for applying optically functional film, optically functional film and production process for the same |
| TW096117770A TWI428422B (en) | 2006-05-19 | 2007-05-18 | Pressure-sensitive adhesive for applying optically functional film, optically functional film and production process for the same |
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| JP2006203589A JP4953717B2 (en) | 2006-05-19 | 2006-07-26 | Optical functional film bonding adhesive, optical functional film and method for producing the same |
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- 2007-05-10 KR KR1020070045544A patent/KR101234931B1/en active IP Right Grant
- 2007-05-10 US US11/746,830 patent/US8388798B2/en active Active
- 2007-05-11 CN CN2007100973769A patent/CN101074349B/en active Active
- 2007-05-18 TW TW096117770A patent/TWI428422B/en active
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| WO2009025360A1 (en) * | 2007-08-22 | 2009-02-26 | Sumitomo Chemical Company, Limited | Composite polarizing plate, laminated optical member, and image display device using them |
| JP2011511100A (en) * | 2008-01-11 | 2011-04-07 | エルジー・ケム・リミテッド | Adhesive composition, polarizing plate containing the same, and liquid crystal display device |
| US9399695B2 (en) | 2008-01-11 | 2016-07-26 | Lg Chem, Ltd. | Pressure-sensitive adhesive compositions, polarizers and liquid crystal displays comprising the same |
| JP2014055299A (en) * | 2008-01-11 | 2014-03-27 | Lg Chem Ltd | Pressure-sensitive adhesive composition, and polarizing plate and liquid crystal display device including the same |
| JP2009198934A (en) * | 2008-02-25 | 2009-09-03 | Daio Paper Corp | Laminate for making name plate |
| JP2009209329A (en) * | 2008-03-06 | 2009-09-17 | Nitto Denko Corp | Light scattering adhesive composition, light scattering adhesive layer, light scattering adhesive sheet, and backlight system using those |
| JP2009227891A (en) * | 2008-03-25 | 2009-10-08 | Mitsubishi Plastics Inc | Self-adhesive sheet |
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| WO2017188428A1 (en) * | 2016-04-28 | 2017-11-02 | 富士フイルム株式会社 | Polarizing plate, method for manufacturing polarizing plate, and liquid crystal display device |
| JPWO2017188428A1 (en) * | 2016-04-28 | 2019-02-21 | 富士フイルム株式会社 | Polarizing plate, manufacturing method of polarizing plate, liquid crystal display device |
| US10816848B2 (en) | 2016-04-28 | 2020-10-27 | Fujifilm Corporation | Polarizing plate, and method for manufacturing polarizing plate including bonding optical rotary layer to polarizer and adjusting storage elastic modulus of bonding layer |
| JP2021121666A (en) * | 2016-12-27 | 2021-08-26 | リンテック株式会社 | Pressure-sensitive adhesive sheet and liquid crystal display member |
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| JP2020070313A (en) * | 2018-10-29 | 2020-05-07 | リンテック株式会社 | Scattering prevention adhesive sheet |
| JP2022536080A (en) * | 2019-06-20 | 2022-08-12 | シャンジン オプトエレクトロニクス（スジョウ） カンパニー リミテッド | Radical adhesive composition, protective film for polarizing plate containing the same, polarizing plate containing the same, and image display device containing the same |
| JP7395096B2 (en) | 2019-06-20 | 2023-12-11 | 杉金光電（南京）有限公司 | A radical adhesive composition, a protective film for a polarizing plate containing the same, a polarizing plate containing the same, and an image display device containing the same |
| JP7099641B2 (en) | 2019-08-30 | 2022-07-12 | Dic株式会社 | Adhesive tape |
| JPWO2021039878A1 (en) * | 2019-08-30 | 2021-03-04 | ||
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| JP2023515454A (en) * | 2020-10-16 | 2023-04-13 | エルジー・ケム・リミテッド | Polarizing plate for display device and display device provided with the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI428422B (en) | 2014-03-01 |
| US8388798B2 (en) | 2013-03-05 |
| TW200804556A (en) | 2008-01-16 |
| KR101234931B1 (en) | 2013-02-19 |
| KR20070111988A (en) | 2007-11-22 |
| CN101074349B (en) | 2011-03-30 |
| CN101074349A (en) | 2007-11-21 |
| JP4953717B2 (en) | 2012-06-13 |
| US20070267133A1 (en) | 2007-11-22 |
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